JP5276916B2 - Dental two-paste self-adhesive resin cement - Google Patents

Description

  The present invention relates to a self-adhesive resin cement. More specifically, the present invention relates to the enamel and ivory of living hard tissues, particularly natural teeth, without pretreatment with conventionally used dental primer, porcelain primer, ceramic primer or metal primer. This is a resin cement in which adhesiveness is imparted to each adherend when a dental prosthetic restoration material made of ceramics, composite resin or metal material is bonded to a substrate such as quality. Furthermore, the present invention relates to a composite type self-adhesive resin cement in which the resin cement paste has excellent physical properties.

  Resin cement generally used in dentistry is roughly classified into a composite type and a PMMA type, but the present invention is limited to a composite type excellent in physical properties of the resin cement body. In recent years, resin cements are highly demanded for bonding aesthetic dental prosthetic restoration materials, and are composed of organic, inorganic and / or organic-inorganic composite materials and polymerizable monomers and oligomers. In order to achieve material strength, the filling factor of the filler is approximately 50% by weight or more. Further, since the polymer is cured even in a region where light does not reach, a dual cure type having a chemical polymerization function is mainstream in addition to photopolymerization.

  In general, a method of bonding a crown, a bridge, an inlay, an onlay, or the like made of ceramics, a composite resin, or a metal material using a resin cement is used to repair a tooth that has been damaged by caries or the like. At this time, a pretreatment material called a primer is used to strengthen the adhesion of the resin cement to the hard tissue of the teeth. This resin cement is required to have sufficient adhesive strength and material strength. Otherwise, the restoration may fall out due to long-term use in a harsh oral environment, creating gaps at the interface between the resin cement and the dentine, and bacteria may invade from it, adversely affecting the dental pulp. It is because there is a possibility of giving.

  The dental hard tissue consists of enamel and dentin, and clinically requires adhesion of resin cement to both. Conventionally, for the purpose of improving adhesiveness, a primer for pretreating the surface of a tooth has been used prior to application of a resin cement. The function of such a primer decalcifies the tooth surface and makes it easy for the resin cement to enter the fine rough surface. Thereafter, an adhesive mechanism in which the resin cement is cured by chemical polymerization or photopolymerization is conceivable.

  On the other hand, the resin cement has conventionally been a powder liquid type, but in order to avoid the complication of the kneading operation, there is an increasing demand for a resin cement that is made into a paste in advance and kneaded the two forms. Such an operation of kneading the paste with the paste is a preferable mode for clinicians because the kneading time is shortened and there are few individual differences among surgeons as compared with powder liquid kneading. Furthermore, such resin cement is used in addition to photopolymerization so that it can be used for prosthetic restoration materials with high light transmission properties such as dental porcelain in addition to prosthetic restoration materials with low light transmission properties such as dental alloys. Therefore, it is desired to have a chemical curing function by chemical polymerization, that is, dual cure.

  However, prior to adhesion with the resin cement, various adherends of tooth, ceramics, composite resin and metal had to be treated in advance with a primer dedicated to each adherend. In clinical practice, a simple adhesion operation that does not require primer treatment is desired for such various adherends.

  In US Pat. No. 6,057,049, at least one multifunctional monomer containing acid is present in a concentration range of about 10% to about 85% by weight and non-reactive filler is about 1% to about A polymerizable composite comprising a polymerization system in a concentration range of about 1.5% to 25% by weight and water in a concentration range of about 0.1% to 25% by weight in a concentration range of 80% by weight. The material, a self-adhesive resin cement that does not require a primer, is disclosed, but since such a composition uses a single acidic monomer, enamel and organic components rich in inorganic components and moisture It is not possible to obtain sufficient adhesion to both dentin.

  Patent Document 2 discloses a two-paste self-adhesive dental material comprising a polymerizable monomer having an acid group, a polymerizable monomer having no acid group, a fine particle filler, a reducing agent, and an oxidizing agent. A method of supplying a composition is disclosed. Specifically, it is assumed that the ratio of the paste having a high content of polymerizable monomers having acidic groups distributed to two and the paste having a low content of monomers having acidic groups is greater than 1: 1. Yes. If the ratio of the paste is changed, the paste supply device becomes complicated.

  Patent Document 3 and Patent Document 5 disclose a self-adhesive dental cement composition composed of a liquid and a powder. However, a liquid and a powder, that is, a powder-liquid type resin cement is more than a paste and paste type. Inferior operability during kneading.

  In Patent Document 4, as a polymerizable monomer containing a special carboxylic acid group, a carboxylic acid compound having one (meth) acryloyl group and one carboxyl group bonded to an aromatic is essential as an adhesive component. Although a dental adhesive composition has been disclosed, a polymerizable monomer containing such a carboxylic acid group cannot provide sufficient adhesion to clinical enamel.

  Patent Document 6 discloses a resin cement containing a metal salt of barbituric acid, an organic peroxide, and an amine as a curing agent. However, this resin cement needs to be pretreated with a dedicated primer in advance for the tooth.

Special table 2006-512466 European Patent Application Publication No. 1502569A1 JP 2000-53518 A JP-A-2005-65902 International Publication Number WO 02 / 092021A1 PCT / JP2006 / 301845 specification

  The present invention has been made in view of such a current situation, and various adherends having different properties such as enamel and dentin teeth, ceramics such as zirconia and alumina, porcelain, and metals. On the other hand, an object of the present invention is to provide a dental self-adhesive resin cement having clinically acceptable adhesion without pretreatment with a primer.

As a result of intensive research on a resin cement paste that does not require a primer, the present inventors have obtained the following components:
(A) a radically polymerizable monomer,
(B) a polymerizable monomer having a phosphonic acid group and / or a phosphate ester group,
(C) a polymerizable monomer having a carboxyl group of a dibasic acid,
A dental two-paste type self-adhesive composite resin cement containing (d) a filler and (e) a polymerization catalyst and not containing water solves the problems of the prior art, and is a hard tissue, especially enamel It has been found that strong adhesion can be imparted to a substrate, dentin substrate, ceramics, composite resin, and metal without the treatment of a primer, and the present invention has been completed. That is, in a polymerizable monomer having an acid group that promotes adhesion, which is called an adhesive monomer, a polymerizable monomer having a functional group such as phosphonic acid or phosphate ester and a carboxyl group having a dibasic acid carboxyl group. It was found that when blended in a combination of monomers, the adhesiveness superior to that of each of them alone was exhibited, that is, a synergistic effect was exhibited, and the present invention was completed.

Specifically, the present invention provides:
(1) (a) a radical polymerizable monomer,
(B) a polymerizable monomer having a phosphonic acid group and / or a phosphate ester group,
(C) a polymerizable monomer having a carboxyl group of a dibasic acid,
A dental two-paste self-adhesive composite resin cement containing (d) a filler, and (e) a polymerization catalyst;
(2) A dental two-paste self-adhesive composite resin cement comprising a first paste and a second paste,
The first paste is (a) a radical polymerizable monomer,
(D) a filler, and (e)-(1) a polymerization accelerator,
The second paste is (a) a radical polymerizable monomer,
(B) a polymerizable monomer having a phosphonic acid group and / or a phosphate ester group,
(C) a polymerizable monomer having a carboxyl group of a dibasic acid,
A dental two-paste self-adhesive composite resin cement according to (1), comprising (d) a filler, and (e)-(2) a polymerization initiator, and none of the pastes contains water;
(3) Component (b) The polymerizable monomer having a phosphonic acid group and / or a phosphoric ester group is represented by the general formula [I]:

（式中、Ｒ_１は水素原子またはメチル基を示し、Ｒ_２は炭素原子数５〜１０のアルキレン基を示し、Ｒ_３は炭素原子数１〜６のアルキレン基を示す）
で示されるホスホン酸基を有する重合性単量体である前記（１）または（２）記載の歯科用ツーペースト型自己接着性コンポジットレジンセメント；
（４）第一のペーストの成分（ｅ）−（１）がバルビツール酸のアルカリまたはアルカリ土類金属塩および／または芳香族第二級または第三級アミンである前記（２）または（３）記載の歯科用ツーペースト型自己接着性コンポジットレジンセメント；
（５）第二のペーストの成分（ｅ）−（２）が化学重合開始剤および／または光重合開始剤である前記（２）ないし（４）のいずれか１に記載の歯科用ツーペースト型自己接着性コンポジットレジンセメント；
（６）前記（１）ないし（５）のいずれか１に記載の組成物が、歯質、歯科用陶材、ジルコニア、コンポジットレジンおよび金合金のすべてに対して有効な剪断接着強度または引張接着強度を示す歯科用ツーペースト型自己接着性コンポジットレジンセメント；
（７）さらに、成分（ｆ）棚寿命安定剤を含む前記（６）記載の歯科用ツーペースト型自己接着性コンポジットレジンセメント；
（８）第一のペーストが、第一のペースト５０重量％に対して
（ａ）ラジカル重合性単量体８.０〜２２.５重量％、
（ｄ）充填剤２７.４５〜４０.０重量％、および
（ｅ）−（１）バルビツール酸のアルカリまたはアルカリ土類金属塩０.０２５〜２.０重量％および／または芳香族第二級または第三級アミン０.０２５〜０.５重量％
を含み、
第二のペーストが、第二のペースト５０重量％に対して
（ａ）ラジカル重合性単量体５.０〜２２.５重量％、
（ｂ）ホスホン酸基および／またはリン酸エステル基を有する重合性単量体０.０５〜３.０重量％、
（ｃ）２塩基酸のカルボキシル基を有する重合性単量体０.０５〜３.０重量％、
（ｄ）充填剤２７.３〜４０.０重量％、および
（ｅ）−（２）化学重合開始剤および／または光重合開始剤０.１〜１.０重量％
を含み、かつ、いずれのペーストも水を含まない、歯質、歯科用陶材、ジルコニア、コンポジットレジンおよび金合金のすべてに対して有効な剪断接着強度または引張接着強度を示す歯科用ツーペースト型自己接着性コンポジットレジンセメント；
を提供する。

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 5 to 10 carbon atoms, and R ₃ represents an alkylene group having 1 to 6 carbon atoms)
The dental two-paste self-adhesive composite resin cement according to (1) or (2), which is a polymerizable monomer having a phosphonic acid group represented by:
(4) The component (e)-(1) of the first paste is an alkali or alkaline earth metal salt of barbituric acid and / or an aromatic secondary or tertiary amine (2) or (3 ) Dental two-paste self-adhesive composite resin cement as described above;
(5) The dental two-paste mold according to any one of (2) to (4), wherein component (e)-(2) of the second paste is a chemical polymerization initiator and / or a photopolymerization initiator. Self-adhesive composite resin cement;
(6) The shear bond strength or tensile bond in which the composition according to any one of the above (1) to (5) is effective for all of dental materials, dental porcelain, zirconia, composite resin and gold alloy Dental two-paste self-adhesive composite resin cement showing strength;
(7) The dental two-paste self-adhesive composite resin cement according to (6), further comprising a component (f) shelf life stabilizer;
(8) The first paste is (a) radically polymerizable monomer 8.0 to 22.5% by weight with respect to 50% by weight of the first paste.
(D) 27.45 to 40.0% by weight of filler and (e)-(1) 0.025 to 2.0% by weight of alkali or alkaline earth metal salt of barbituric acid and / or aromatic second Grades or tertiary amines 0.025 to 0.5% by weight
Including
The second paste comprises (a) a radical polymerizable monomer (5.0 to 22.5% by weight) with respect to 50% by weight of the second paste,
(B) 0.05 to 3.0% by weight of a polymerizable monomer having a phosphonic acid group and / or a phosphoric acid ester group,
(C) 0.05 to 3.0% by weight of a polymerizable monomer having a carboxyl group of a dibasic acid,
(D) 27.3 to 40.0% by weight of filler, and (e)-(2) 0.1 to 1.0% by weight of chemical polymerization initiator and / or photopolymerization initiator.
Dental two-paste molds that exhibit effective shear or tensile adhesive strength for all of the dentin, dental porcelain, zirconia, composite resin and gold alloy, including Self-adhesive composite resin cement;
I will provide a.

  The dental two-paste type self-adhesive composite resin cement of the present invention can be applied to dental materials such as enamel and dentin, dental ceramics, composite resins and metals without using a primer specific to the adherend. And has sufficient adhesion.

  The component (a) radical polymerizable monomer used in the dental two-paste type self-adhesive composite resin cement (hereinafter referred to as “resin cement”) of the present invention is a radical polymerizable monomer containing no acid group. Are used, for example, (meth) acrylic acid ester derivatives, alkylene glycol di (meth) acrylates, alkyl di (meth) acrylates, epoxy di (meth) acrylates, bisphenol A-alkyl di (meth) acrylates, urethane di ( (Meth) acrylates, urethane tri (meth) acrylates, urethane tetra (meth) acrylates, hydroxyalkyl (meth) acrylates, (meth) acrylates having an Si group, SH group or —SS—group (Meth) acrylates, styrene derivatives It is below. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, di-2-methacryloyloxyethyl-2,2,4-trimethyl Hexamethylene dicarbamate, 2,2′-bis [4- (3- (meth) acryloyloxy-2-hydroxypropoxy) phenyl] propane, di (meth) acryloxyisophorone dicarbamate, 2-hydroxyethyl (meth) acrylate , 6-hydroxyhexyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol di (meth) acrylate, γ-methacryloxypropyltrimethoxysilane and the like. Particularly suitable radical polymerizable monomers are ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, 1,6-hexanedi (meth) acrylate, di (meth). Acryloxyethyl-2,2,4-trimethylhexamethylene diurethane, di (meth) acryloxyisophorone diurethane, 2,2′-bis [4- (3- (meth) acryloyloxy-2-hydroxypropoxy) phenyl] Propane, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol di (meth) acrylate and the like, among others ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, di -2 Methacryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate, 2,2′-bis [4- (3- (meth) acryloyloxy-2-hydroxypropoxy) phenyl] propane and 2-hydroxyethyl (meta ) Acrylate is particularly preferred. These radically polymerizable monomers can be used alone or in admixture of two or more.

  The compounding amount of the component (a) radical polymerizable monomer in the resin cement of the present invention is usually 13.0 to 45.0% by weight, preferably 15.5%, based on the total amount of the composition obtained by mixing the two pastes. 0 to 40.0% by weight, more preferably 20.0 to 35.0% by weight. If it is less than 13.0% by weight, the viscosity of the paste becomes too high, whereas if it exceeds 45.0% by weight, the viscosity of the paste is too high. Is too low, and paste properties suitable for use as a resin cement cannot be obtained.

  Examples of the component (b) polymerizable monomer having a phosphonic acid group and / or a phosphoric ester group used in the resin cement of the present invention include those represented by the general formula [I]:

（式中、Ｒ_１は水素原子またはメチル基を示し、Ｒ_２は炭素原子数５〜１０のアルキレン基を示し、Ｒ_３は炭素原子数１〜６のアルキレン基を示す）
で示される重合性単量体が挙げられる。

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 5 to 10 carbon atoms, and R ₃ represents an alkylene group having 1 to 6 carbon atoms)
The polymerizable monomer shown by these is mentioned.

  Specific examples of the compound represented by the general formula [I] include the following compounds.

  In addition to the compound [I], the component (b) used in the resin cement of the present invention has a phosphate group such as 2- (methacryloxy) ethyl phosphate and bis [2- (methacryloxy) ethyl] phosphate. A polymerizable monomer is also effective.

  The compounding amount of the component (b) polymerizable monomer having a phosphonic acid group and / or a phosphoric ester group in the resin cement of the present invention is usually 0.05 with respect to the total amount of the composition in which two pastes are mixed. .About.3.0% by weight, preferably 0.2.about.3.0% by weight, more preferably 0.3.about.2.0% by weight, and less than 0.05% by weight adheres to all adherends. On the other hand, if it exceeds 3.0% by weight, the adhesion to dentin is lowered.

  Examples of the polymerizable monomer having a carboxyl group of component (c) dibasic acid used in the resin cement of the present invention include 1,4-di (meth) acryloxyethyl pyromellitic acid, 4- (meth) Acryloxybutyl trimellitic acid, 4- (meth) acryloxyhexyl trimellitic acid, 4- (meth) acryloxydecyl trimellitic acid, 4-acryloxybutyl trimellitic acid, 11- (meth) acryloxy-1,1 -Undecanedicarboxylic acid and the like can be mentioned, and 4- (meth) acryloxyethyl trimellitic acid and 4- (meth) acryloxyethyl trimellitic anhydride are particularly preferable.

  In the resin cement of the present invention, the amount of the component (c) polymerizable monomer having a carboxyl group of dibasic acid and an acid anhydride residue is usually 0 with respect to the total amount of the composition in which the paste of 2 is mixed. 0.05 to 5.0% by weight, preferably 0.2 to 3.0% by weight, more preferably 0.3 to 2.0% by weight, and less than 0.05% by weight adheres to all adherends. On the other hand, if it exceeds 5.0% by weight, the solubility of the polymerizable monomer is lowered.

  Examples of the component (d) filler used in the resin cement of the present invention include known organic fillers, inorganic fillers, and organic / inorganic composite fillers.

  For example, a fluoroaluminosilicate glass filler, which is a known inorganic filler, can be produced by a known glass production method, but is preferably produced by a melting method or a sol-gel method.

  Examples of the melting method include silica, alumina, aluminum hydroxide, aluminum oxalate, mullite, calcium oxalate, strontium oxalate, sodium oxalate, sodium carbonate, calcium fluoride, aluminum fluoride, strontium fluoride, and phosphoric acid. A glass raw material selected from aluminum, sodium phosphate and the like can be manufactured by melting at a high temperature of 1000 ° C. or higher, cooling, and pulverizing.

  Preferred compositions for the fluoroaluminosilicate glass that can be used in the resin cement of the present invention are as follows:

The amount of fluorine contained in these glasses is preferably 5 to 60 mol%.
In the above composition, calcium oxide is used, but any alkaline earth metal oxide can be used. At least a portion of the alkaline earth metal may be replaced with a lanthanide metal such as lanthanum, gadolinium, or ytterbium. Furthermore, among these glasses, some or all of the alumina may be replaced with a Group III metal other than aluminum. Similarly, part of silica in the glass may be replaced with zirconium oxide or titanium oxide. If the glass contains strontium, lanthanum, gadolinium, ytterbium or zirconium, the glass becomes radiopaque.

Moreover, as the sol-gel method, for example, a first solution containing a soluble aluminum compound and a soluble silicon compound is reacted with a second solution containing a Group II metal soluble compound, and the resulting gel is heat-dried. Alternatively, a method of recovering by drying by freeze-drying can be mentioned. When this method is used, it is possible to avoid the use of additives used in the production of ordinary glass such as a fluxing agent and to use a relatively low temperature. For this reason, glass with higher transparency than before can be obtained.
Further, another compound such as an organic metal or an inorganic salt alcohol solution may be added at the sol stage to obtain a glass containing a divalent or trivalent metal ion.
An acidic or basic solvent may also be added to the sol-gel reaction mixture to increase the gelation rate. By this method, a refractory glass homogeneous at a relatively low temperature can be obtained.

This sol-gel method is particularly suitable for the production of glass incorporating gadolinium and the following five components:
_{X n O m -CaO-Al 2} O 3 -SiO 2 -F
(Wherein X _n O _m is an oxide of radiopaque material, for example Gd ₂ O ₃ )
Such a five-component glass is difficult to manufacture. However, according to the sol-gel method, glass can be easily produced. Aluminum secondary butoxide (Asb) in ethanol and isobutyl alcohol as the CaO source, tetraethyl silicate as the SiO ₂ source, 40% hydrofluoric acid as the F source, and ethanol-soluble Gd (NO ₃ ) ₃ as the Gd ₂ O ₃ source Alternatively, it may be replaced with a methanol solution.

Further, calcium oxide may be replaced with anhydrous Ca (NO ₃ ) ₂ dissolved in ethanol at 50 ° C. These solutions are mixed while stirring at 50 ° C. This may then be refluxed at 70 ° C. After drying, the material is ground while still soft and then dried at a temperature of 400 to 500 ° C. This is further pulverized to the required size.

  As the component (d) filler, one having an average particle diameter of 0.1 to 10 μm can be used. Preferably it is 0.1-5 micrometers. The filler is preferably subjected to silane treatment by a conventional method for the purpose of improving the affinity with a resin component such as a polymerizable monomer. Examples of the silane treatment agent used include vinyltrimethoxysilane, vinylethoxysilane, vinyltrichlorosilane, γ-methacryloyloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane. .

  The blending amount of the component (d) filler in the resin cement of the present invention is usually 54.75 to 80.0% by weight, preferably 57.0 to 77.% by weight based on the total amount of the composition in which the two pastes are mixed. 0% by weight. If the amount is less than 54.75% by weight, the filler is precipitated and a so-called liquid floating phenomenon occurs. On the other hand, if the amount exceeds 80.0% by weight, the fluidity of the paste becomes extremely poor and the function as a cement is lowered.

The component (e) polymerization catalyst used in the resin cement of the present invention comprises a polymerization accelerator ((e)-(1)) and a polymerization initiator ((e)-(2)). It consists of a chemical polymerization initiator and a photopolymerization initiator.
Among these, examples of the polymerization accelerator include alkali or alkaline earth metal salts of barbituric acid and aromatic secondary amines or tertiary amines.
Examples of alkali or alkaline earth metal salts of barbituric acid include, for example, 5-n-butyl barbituric acid sodium salt, 5-n-butyl barbituric acid calcium salt, 1-benzyl-5-phenylbarbituric acid sodium salt 1-benzyl-5-phenylbarbituric acid calcium salt, 1,3,5-trimethylbarbituric acid sodium salt, 1,3,5-trimethylbarbituric acid calcium salt, and the like.
In the resin cement of the present invention, the blending amount of the component (e)-(1) alkali or alkaline earth metal salt of barbituric acid is usually 0.025 to 3 with respect to the total amount of the composition in which the paste of 2 is mixed. It is 0.0 weight%, Preferably it is 0.1-2.0 weight%, More preferably, it is 0.7-1.5 weight%. When the amount is less than 0.025% by weight, the curing becomes insufficient. On the other hand, when the amount exceeds 3.0% by weight, the curing proceeds rapidly, so that an appropriate working time cannot be obtained.

Examples of the component (e)-(1) aromatic secondary amine or tertiary amine in the resin cement of the present invention include N-dimethylaniline, N-dimethyl-p-toluidine, N, N-di ( 2-hydroxyethyl) -p-toluidine, N-methyl-p-toluidine and the like.
The compounding amount of the component (e)-(1) aromatic secondary amine or tertiary amine in the resin cement of the present invention is usually from 0.025 to 1 with respect to the total amount of the composition obtained by mixing the two pastes. It is 0% by weight, preferably 0.1-0.8% by weight, more preferably 0.1-0.5% by weight. When the amount is less than 0.025% by weight, curing is insufficient. On the other hand, when the amount exceeds 1.0% by weight, curing proceeds rapidly, so that an appropriate working time cannot be obtained.

  Moreover, as a chemical polymerization initiator among components (e)-(2) polymerization initiators in the resin cement of the present invention, for example, the following organic peroxides: benzoyl peroxide, 4,4′-dichlorobenzoic peroxide 2,4-dichlorobenzoyl peroxide, dilauryl peroxide, methyl ethyl ketone peroxide, t-butylperoxymaleic acid and succinic acid and peroxides, etc. are particularly preferred, t-butylperoxymaleic acid, peroxysuccinic acid And 4,4′-dichlorobenzoyl peroxide.

  Among the components (e)-(2) polymerization initiators in the resin cement of the present invention, examples of the photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin, benzophenone, thioxanthone, 2- Chlorothioxanthone, 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy-N, N, N-trimethyl-1-propanealuminum chloride, 9,10-anthraquinone, camphorquinone, benzyl, Examples thereof include ultraviolet sensitizers such as 4,4'-dicyclobenzyl, diacetyl, (bis) acylphosphine oxide, and monoacylphosphine oxides, and visible light sensitizers.

  The compounding amount of the component (e)-(2) polymerization initiator in the resin cement of the present invention is usually 0.05 to 2.0% by weight, preferably 0, based on the total amount of the composition in which the paste of 2 is mixed. It is 0.1 to 1.5% by weight, more preferably 0.1 to 1.0% by weight. If the amount is less than 0.05% by weight, the curing becomes insufficient. On the other hand, if the amount exceeds 2.0% by weight, the curing proceeds rapidly, so that an appropriate working time cannot be obtained.

  The resin cement of the present invention is used by mixing the first paste and the second paste, and preferably hardens in 100 to 600 seconds after mixing. If the curing time is less than 100 seconds, the time required for the work cannot be obtained, while if it exceeds 600 seconds, the burden on the patient increases.

  Examples of the component (f) shelf life stabilizer used in the resin cement of the present invention include hydroquinone, hydroquinone monomethyl ether, hydroxymethoxybenzophenone, butylated hydroxytoluene and the like.

  The blending amount of the component (f) shelf life stabilizer in the resin cement of the present invention is usually from 0.02 to 0.2% by weight, preferably from 0.03 to 0.2% by weight based on the total amount of the composition obtained by mixing the two pastes. 0.06% by weight. When the amount is less than 0.02% by weight, the shelf life of the paste becomes insufficient. On the other hand, when the amount exceeds 0.2% by weight, sufficient curing cannot be obtained.

The resin cement of the present invention is a two-paste type, and is composed of a first paste and a second paste, and the effect of the resin cement can be achieved by mixing both at the time of use. The mixing ratio of the first paste to the second paste is usually 1: 7 to 7: 1, preferably 1: 4 to 4: 1, more preferably 1: 2 to 2: 1, most preferably by weight ratio. Is 1: 1.
Since the resin cement of the present invention begins to harden when these polymerization accelerators ((e)-(1)) and polymerization initiators ((e)-(2)) are mixed, they are separated into two pastes until use. It is necessary to.
Therefore, when mix | blending an above described component with either 1st or 2nd or both, the above-mentioned compounding quantity of the ratio according to both mixing ratio can be mix | blended.

Accordingly, the present invention in one form,
The first paste is (a) a radical polymerizable monomer,
(D) a filler, and (e)-(1) a polymerization accelerator,
The second paste is (a) a radical polymerizable monomer,
(B) a polymerizable monomer having a phosphonic acid group and / or a phosphate ester group,
(C) a polymerizable monomer having a carboxyl group of a dibasic acid,
There is also provided the above resin cement comprising (d) a filler and (e)-(2) a polymerization initiator.

The present invention will be specifically described below, but the present invention is not limited to these examples. In addition, the abbreviations, abbreviations, and adhesive strength measurement methods shown in the examples are as follows.
[Radically polymerizable monomer]
UDMA: Di-2-methacryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate 3G: Triethylene glycol dimethacrylate Bis-GMA: 2,2′-bis [4- (3- (meta ) Acryloyloxy-2-hydroxypropoxy) phenyl] propane-2-HEMA
[Polymerizable monomer containing a phosphonic acid group represented by the following general formula [I]]
Formula [I]:

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 5 to 10 carbon atoms, and R ₃ represents an alkylene group having 1 to 6 carbon atoms)
6-MHPA: (6-Methacryloxy) hexylphosphonoacetate The polymerizable monomer represented by the above general formula [I] is produced by the method described in Japanese Patent Publication No. 2865794.
[Polymerizable monomer having a phosphate group]
2-MEP: 2- (methacryloxy) ethyl phosphate Bis-MEP: bis [2- (methacryloxy) ethyl] phosphate [polymerizable monomer having a dibasic acid carboxyl group]
· 4-AET: 4-acryloxyethyl trimellitic acid · 4-MET: 4-methacryloxyethyl trimellitic acid [filler]
-FASG filler: fluoroaluminosilicate glass filler, average particle size 1.8 µm, γ-methacryloyloxypropyltrimethoxysilane 8% silane-treated filler-R-711: ultrafine silica filler [polymerization accelerator]
-BBA-Na: 5-n-butyl barbituric acid sodium salt- BPBA-Ca: 1-benzyl-5-phenylbarbituric acid calcium salt-DEPT: N, N-di (2-hydroxyethyl) -p-toluidine (Polymerization initiator)
・ BPO: benzoyl peroxide ・ CQ: camphorquinone [shelf life stabilizer]
・ BHT: Butylated hydroxytoluene

(1) Measuring method of TG (thermogravimetric) / DTA (differential thermal analysis):
A thermogravimetric / differential thermal analyzer (manufactured by Seiko Denshi Kogyo Co., Ltd.) was used for measurement under the following conditions.
Sample container: Aluminum pan Nitrogen gas: 200 mL / min
Temperature rise: 10 ° C / min
Reference: Alumina

(2) Bond strength measurement method (i) Enamel and dentin bond strength measurement Tooth was replaced with human teeth using freshly extracted bovine front teeth, and after removing their roots, they were embedded with epoxy resin. The lip surface of the bovine teeth was polished under running water using water-resistant polishing paper to expose enamel and dentin. After polishing SiC No. 600, washing and air drying were performed. On the other hand, the adhesion test jig, stainless rod (diameter 4.15 mm) was sandblasted with alumina having a particle size of about 50 μm, washed with water and air-dried, and then the metal primer “Metal Link” [ Made by Matsukaze Co., Ltd.] and naturally dried for 10 seconds. The first paste and the second paste of resin cement each filled in equal amounts in double syringes manufactured by SULZURMIXPAC are kneaded and extruded by passing through an attached static mixer. The extruded paste is interposed between the tooth and the stainless rod, and a load of 200 g is applied and adhered. After the excess paste is removed using a microbrush, light irradiation is performed for 10 seconds along the cement line. As the light irradiator, “Grip Light II” (manufactured by Matsukaze Co., Ltd.) was used. After 10 minutes of light irradiation, the load was removed, and the same adhesion test specimen (n = 6) was immersed in distilled water at 37 ° C. for 24 hours, and then an Instron universal tester (Instron 5567, manufactured by Instron) was used to crosshead. The shear bond strength to the tooth was measured at a speed of 1 mm / min.

(Ii) Measurement of porcelain bond strength Dental porcelain “Vintage Halo” [Made by Matsukaze Co., Ltd.] One flat surface of the fired product (φ11 mm × 8.5 mm) is polished with SiC No. 600, washed with water and air-dried to obtain a particle size of about After sandblasting (0.1 to 0.2 MPa) using 50 μm of alumina, it was washed with water and air-dried. On the other hand, a jig for adhesion test, stainless rod (diameter: 4.55 mm), sandblasted the bonded surface using alumina with a particle size of about 50 μm, washed with water and air dried, then metal primer “Metal Link” [stock Made by Matsukaze Co., Ltd.] and naturally dried for 10 seconds. Using a jig for adhesion test and a stainless rod (diameter: 4.55 mm), the tensile adhesion strength to the porcelain was measured in the same manner as (i).

(Iii) Measurement of adhesion strength of zirconia One plane of a zirconia flat plate (15 mm × 15 mm × 1.8 mm) manufactured by Japan Fine Ceramics Co., Ltd. is polished with SiC No. 600, washed with water, air-dried, and then using alumina having a particle size of about 50 μm. After sandblasting (0.2 to 0.3 MPa), it was washed with water and air dried. (Ii) Measurement of the tensile adhesive strength of porcelain and the measurement of the tensile adhesive strength with respect to zirconia by the same method.

(Iv) Measurement of composite resin adhesive strength Place a metal frame with an inner diameter of 15 mm and a height of 2 mm on a cover glass, fill with paste of composite resin “Cera-Mage” (manufactured by Matsukaze Co., Ltd.), and press contact with the cover glass on both upper and lower sides Then, one cover glass surface was turned up, and it irradiated with light for 3 minutes in "twin polymerizer" [made by Matsukaze Co., Ltd.]. The bottom surface was sandblasted (0.1 to 0.2 MPa), then washed with water and air dried. (Ii) Measurement of the tensile adhesive strength of the porcelain and the measurement of the tensile adhesive strength with respect to the composite resin in the same manner.

(V) Gold alloy adhesion strength measurement One side of a flat plate (15 mm x 15 mm x 2.1 mm) of a gold alloy "Super Gold Type 4" (manufactured by Matsukaze Co., Ltd.) is polished with SiC No. 600, washed with water and dried with air, and then the particle size is about Sandblasting (0.4 to 0.5 MPa) was performed using 50 μm alumina, followed by washing with water and air drying. (Ii) Measurement of the tensile adhesive strength of porcelain and the measurement of the tensile adhesive strength with respect to the gold alloy in the same manner.

(3) Measurement of curing time The curing time of the kneaded product of the first paste and the second paste was measured according to ISO 4049: 2000E.
Specifically, 0.8 g of paste kneaded is filled in a sample well (4 mmφ × 6 mm) equipped with a thermocouple, and an exothermic curve due to the curing reaction is recorded. The time from the start of kneading of the paste to the peak of the exothermic curve was taken as the curing time, and the three measurements were averaged.

Production Example 1: Production of sodium 5-n-butylbarbiturate 25 g of distilled water was placed in a 100 mL Erlenmeyer flask, and 3.11 g (29.34 mmol) of anhydrous sodium carbonate was added with stirring, and dissolved in a 30 ° C. hot water bath. To obtain an aqueous Na ₂ CO ₃ solution.
Separately, 20 g of distilled water was weighed into a 200 mL beaker, and while stirring, 10.82 g (58.74 mmol) of 5-n-butylbarbituric acid (BBA) was added and dispersed uniformly to obtain a BBA suspension. It was.
An aqueous Na ₂ CO ₃ solution was slowly added to the BBA suspension, and the mixture was reacted in an approximately 30 ° C. hot water bath with stirring for 1 hour. Then, it concentrated to about 40 g with an evaporator at 70 cmHg in a hot water bath at 40 ° C. to 50 ° C. About 200 mL of acetone was added to the residue for crystallization, followed by solid-liquid separation by suction filtration. In order to remove unreacted BBA, the obtained white crystals were sufficiently washed with acetone, and the remaining crystals were vacuum dried to obtain a sodium salt of 5-n-butylbarbituric acid (BBA · Na).
The melting point and decomposition temperature of the obtained salt were measured by thermogravimetric analysis (TG) and thermal differential analysis (DTA). Further, the pH of a 2% by weight aqueous solution of the obtained salt was measured. As a result, it was confirmed that pure barbiturate was produced.

Production Example 2: Production of sodium 1-benzyl-5-phenylbarbiturate 25 g of distilled water was placed in a 100 mL Erlenmeyer flask, and 3.11 g (29.34 mmol) of anhydrous sodium carbonate was added with stirring, in a 30 ° C. water bath. To obtain an aqueous Na ₂ CO ₃ solution.
Separately, 40 g of distilled water and 6 g of acetone are put into a 200 mL beaker, and while stirring, 17.29 g (58.74 mmol) of 1-benzyl-5-phenylbarbituric acid (BPBA) is added and dispersed uniformly. An aqueous solution was obtained.
An aqueous Na ₂ CO ₃ solution was slowly added to an aqueous BPBA acetone solution and allowed to react for 1 hour in an approximately 30 ° C. hot water bath with stirring. Then, it concentrated to about 40g with an evaporator at 70 cmHg in a 40-50 degreeC hot water bath. About 200 mL of acetone was added to the residue for crystallization, followed by solid-liquid separation by suction filtration. In order to remove unreacted BPBA, the obtained white crystals were thoroughly washed with acetone, and the remaining crystals were vacuum-dried to obtain 1-benzyl-5-phenylbarbituric acid sodium salt (BPBA · Na). It was.
The melting point and decomposition temperature of the obtained salt were measured by thermogravimetric analysis (TG) and thermal differential analysis (DTA). Further, the pH of a 2% by weight aqueous solution of the obtained salt was measured. As a result, it was confirmed that pure barbiturate was produced.

  The measurement results of Production Examples 1 and 2 are shown in Table 1.

Example 1: Effect of resin cement composition on resin cement properties (1)
(1) Production of Resin Cement Based on the composition shown in Table 2, two-paste resin cements 1 to 5 made of the first paste and the second paste were produced. In this example, the total amount of each of the first paste and the second paste other than the shelf life stabilizer that is component (f) is 50 parts by weight with respect to the entire resin cement composition, and an appropriate amount of components ( f) was added.

(2) Characteristic evaluation of resin cement [adhesive strength]
For the resin cements 1 to 5, the shear bond strength to the tooth (enamel and dentin) specimens and the tensile adhesive strength to each specimen of zirconia, porcelain, composite resin and gold alloy were measured. Table 3 shows the measurement results.

Resin cement 1 contains 4-AET component (c), but no component (b), resin cement 2 does not contain component (c), contains 2-MEP component (b), and resin cement 3 Includes both components (c) and (b) (4-AET and 2-MEP). In this case, a remarkable synergistic effect was recognized in components (c) and (b) in the adhesion strength to enamel.
Similarly, resin cement 4 contains 4-MET as component (c), but no component (b), resin cement 2 does not contain component (c), and contains 2-MEP as component (b), The resin cement 5 contains both components (c) and (b) (4-MET and 2-MEP). In this case, a synergistic effect was recognized in components (c) and (b) in the adhesive strength to zirconia.

Example 2: Effect of resin cement composition on resin cement properties (2)
(1) Production of Resin Cement Based on the composition shown in Table 4, two-paste resin cements 6 to 10 comprising a first paste and a second paste were produced. In this example, the total amount of each of the first paste and the second paste other than the shelf life stabilizer that is component (f) is 50 parts by weight with respect to the entire resin cement composition, and an appropriate amount of components ( f) was added.

(2) Characteristic evaluation of resin cement [adhesive strength]
For the resin cements 6 to 10, the shear bond strength to the tooth (enamel and dentin) specimens and the tensile adhesive strength to each specimen of zirconia, porcelain, composite resin and gold alloy were measured. Table 5 shows the measurement results.

Resin cement 6 contains 4-AET as component (c) but no component (b), cement 7 does not have component (c), contains Bis-MEP as component (b), and cement 8 contains component It includes both components (c) and (b) (4-AET and Bis-MEP). In this case, a remarkable synergistic effect was recognized in components (c) and (b) in enamel bond strength.
Similarly, cement 9 contains 4-MET as component (c) but no component (b), cement 6 contains component (c) and contains Bis-MEP (b), and cement 10 contains component (c). It contains both components (c) and (b) (4-MET and Bis-MEP). Also in this case, a remarkable synergistic effect was recognized in components (c) and (b) in enamel bond strength.

Example 3: Effect of resin cement composition on resin cement properties (3)
(1) Production of Resin Cement Based on the composition shown in Table 6, two-paste resin cements 11 to 15 made of the first paste and the second paste were produced. In this example, the total amount of each of the first paste and the second paste other than the shelf life stabilizer that is component (f) is 50 parts by weight with respect to the entire resin cement composition, and an appropriate amount of components ( f) was added.

(2) Characteristic evaluation of resin cement [adhesive strength]
For the resin cements 11 to 15, the shear bond strength to the tooth (enamel and dentin) specimens and the tensile adhesive strength to each specimen of zirconia, porcelain, composite resin and gold alloy were measured. Table 7 shows the measurement results.

Resin cement 11 contains 4-AET as component (c) but no component (b), resin cement 12 does not contain component (c), contains component (b) 6-MHPA, and resin cement 13 contains component It includes both components (c) and (b) (4-AET and 6-MHPA). In this case, a synergistic effect was observed in components (c) and (b) in dentin bond strength.
Similarly, resin cement 14 contains 4-MET as component (c) but no component (b), and resin cement 12 does not contain component (c) and contains 6-MHPA as component (b). The cement 15 includes both components (c) and (b) (4-MET and 6-MHPA). In this case, a remarkable synergistic effect was recognized in components (c) and (b) in the enamel and dentin bond strength.

Example 4: Effect of resin cement composition on resin cement properties (4)
(1) Manufacture of resin cement Based on the composition of Table 8, two-paste resin cements 16 to 21 composed of a first paste and a second paste were manufactured. In this example, the total amount of each of the first paste and the second paste other than the shelf life stabilizer that is component (f) is 50 parts by weight with respect to the entire resin cement composition, and an appropriate amount of components ( f) was added.

(2) Characteristic evaluation of resin cement [adhesive strength]
For the resin cements 16 to 21, the shear bond strength to the tooth (enamel and dentin) specimens and the tensile adhesive strength to each specimen of zirconia, porcelain, composite resin and gold alloy were measured. Table 9 shows the measurement results.
[Curing time]
The setting time of the resin cements 16 to 21 was measured. Table 9 shows the measurement results.

From the characteristic evaluation of the resin cement 16, it was found that if the salt of the barbituric acid of the component (e)-(1) is missing, the adhesive strength is lowered and the curing time is lengthened.
Further, by comparing the resin cements 17 to 21, it was found that any of the resin cements had good adhesive strength and curing time.
Thereby, it was confirmed that the optimal range of content of the salt of barbituric acid of component (e)-(1) is 0.1 part by weight to 2.0 parts by weight.

Example 5: Effect of resin cement composition on resin cement properties (5)
(1) Manufacture of resin cement Based on the composition of Table 10, two-paste resin cements 22 to 27 made of a first paste and a second paste were manufactured. In this example, the total amount of each of the first paste and the second paste other than the shelf life stabilizer that is component (f) is 50 parts by weight with respect to the entire resin cement composition, and an appropriate amount of components ( f) was added.

(2) Characteristic evaluation of resin cement [adhesive strength]
For the resin cements 22 to 27, the shear bond strength to the tooth (enamel and dentin) specimens and the tensile adhesive strength to each specimen of zirconia, porcelain, composite resin and gold alloy were measured. Table 11 shows the measurement results.
[Curing time]
The curing time of the resin cements 22 to 27 was measured. Table 11 shows the measurement results.

From the characteristic evaluation of the resin cement 22, it was found that if the amine of the component (e)-(1) is missing, the adhesive strength is lowered and the curing time becomes extremely long.
In addition, a comparison of the resin cements 23 to 27 revealed that when the content of the amine of the component (e)-(1) is increased, the curing time is shortened and sufficient adhesion operability cannot be obtained.
The resin cement 26 had a short setting time, and sufficient adhesion operability was not obtained. Further, in the resin cement 27, since the curing time was short, measurement data of the adhesive strength and the curing time could not be obtained.
Thereby, it was confirmed that the optimal range of content of the amine of component (e)-(1) is 0.1 part by weight to 0.5 part by weight.

Example 6: Effect of resin cement composition on resin cement properties (6)
(1) Production of Resin Cement Based on the composition shown in Table 12, two-paste resin cements 28 to 33 each comprising a first paste and a second paste were produced. In this example, the total amount of each of the first paste and the second paste other than the shelf life stabilizer that is component (f) is 50 parts by weight with respect to the entire resin cement composition, and an appropriate amount of components ( f) was added.

(2) Characteristic evaluation of resin cement [adhesive strength]
For the resin cements 28 to 33, the shear bond strength to the tooth (enamel and dentin) specimens and the tensile adhesive strength to each specimen of zirconia, porcelain, composite resin and gold alloy were measured. Table 13 shows the measurement results.
[Curing time]
The setting time of the resin cements 28 to 33 was measured. Table 13 shows the measurement results.

From the characteristic evaluation of the resin cement 28, it was found that when the organic peroxide of the components (e)-(2) is lacking, the adhesive strength is lowered and the curing time becomes extremely long.
A comparison of the resin cements 29 to 33 showed that when the content of the organic peroxide of the components (e)-(2) was increased, the curing time tended to be shortened, but sufficient adhesive strength was obtained. It was.
Thereby, it was confirmed that the optimal range of content of the organic peroxide of component (e)-(2) is 0.1 weight part-1.0 weight part.

Example 7: Effect of resin cement composition on resin cement properties (7)
(1) Production of Resin Cement Based on the composition shown in Table 14, two-paste resin cements 34 to 38 made of the first paste and the second paste were produced. In this example, the total amount of each of the first paste and the second paste other than the shelf life stabilizer that is component (f) is 50 parts by weight with respect to the entire resin cement composition, and an appropriate amount of components ( f) was added.

(2) Characteristic evaluation of resin cement [adhesive strength]
For the resin cements 34 to 38, the shear bond strength to the tooth (enamel and dentin) specimens and the tensile adhesive strength to each specimen of zirconia, porcelain, composite resin and gold alloy were measured. Table 15 shows the measurement results.

By comparing the resin cements 34 to 38, sufficient adhesive strength can be obtained when the content of the monomer (b) having a phosphonic acid and / or phosphate ester group is 0.2 to 3.0 parts by weight. I understood.
Thereby, it was confirmed that the suitable range of content of the monomer which has a phosphonic acid and / or phosphate ester group of a component (b) is 0.2 weight part-3.0 weight part.

Example 9: Effect of resin cement composition on resin cement properties (8)
(1) Manufacture of resin cement Based on the composition of Table 16, two-paste resin cements 39 to 43 made of the first paste and the second paste were manufactured. In this example, the total amount of each of the first paste and the second paste other than the shelf life stabilizer that is component (f) is 50 parts by weight with respect to the entire resin cement composition, and an appropriate amount of components ( f) was added.

(2) Characteristic evaluation of resin cement [adhesive strength]
For the resin cements 39 to 43, the shear bond strength to the tooth (enamel and dentin) specimens and the tensile adhesive strength to each specimen of zirconia, porcelain, composite resin and gold alloy were measured. Table 17 shows the measurement results.

Comparison of the resin cements 39 to 43 shows that sufficient adhesive strength can be obtained when the content of the monomer having a carboxyl group of the dibasic acid component (c) is 0.2 to 3.0 parts by weight. It was.
Thereby, it was confirmed that the suitable range of content of the monomer which has the carboxyl group of the dibasic acid of a component (c) is 0.2 weight part-3.0 weight part.

  ADVANTAGE OF THE INVENTION According to this invention, the dental material excellent in adhesive strength can be provided, without processing with the primer according to various to-be-adhered bodies.

Claims (6)

(A) a radically polymerizable monomer,
(B) General formula [I]:

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 5 to 10 carbon atoms, and R ₃ represents an alkylene group having 1 to 6 carbon atoms)
A polymerizable monomer having a phosphonic acid group represented by:
(C) a polymerizable monomer having a carboxyl group of a dibasic acid,
A dental two-paste self-adhesive composite resin cement containing (d) a filler and (e) a polymerization catalyst. A dental two-paste type self-adhesive composite resin cement comprising a first paste and a second paste,
The first paste is (a) a radical polymerizable monomer,
(D) a filler, and (e)-(1) a polymerization accelerator,
The second paste is (a) a radical polymerizable monomer,
(B) General formula [I]:

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 5 to 10 carbon atoms, and R ₃ represents an alkylene group having 1 to 6 carbon atoms)
A polymerizable monomer having a phosphonic acid group represented by:
(C) a polymerizable monomer having a carboxyl group of a dibasic acid,
The dental two-paste self-adhesive composite resin cement according to claim 1, comprising (d) a filler, and (e)-(2) a polymerization initiator, and none of the pastes contains water.   Dental two-paste mold according to claim 2, wherein component (e)-(1) of the first paste is an alkali or alkaline earth metal salt of barbituric acid and / or an aromatic secondary or tertiary amine. Self-adhesive composite resin cement.   The dental two-paste self-adhesive composite resin cement according to claim 2 or 3, wherein the component (e)-(2) of the second paste is a chemical polymerization initiator and / or a photopolymerization initiator.   The dental two-paste self-adhesive composite resin cement according to any one of claims 1 to 4, further comprising a component (f) shelf life stabilizer.   The first paste is based on 50% by weight of the first paste
(A) 8.0-22.5% by weight of radically polymerizable monomer,
(D) 27.45 to 40.0% by weight filler, and
(E)-(1) Alkali or alkaline earth metal salt of barbituric acid 0.025 to 2.0% by weight and / or aromatic secondary or tertiary amine 0.025 to 0.5% by weight
Including
  The second paste is based on 50% by weight of the second paste
(A) 5.0-22.5% by weight of radically polymerizable monomer,
(B) General formula [I]:

(Wherein R ₁ Represents a hydrogen atom or a methyl group, R ₂ Represents an alkylene group having 5 to 10 carbon atoms, and R ₃ Represents an alkylene group having 1 to 6 carbon atoms)
A polymerizable monomer having a phosphonic acid group represented by the formula of 0.05 to 3.0% by weight,
(C) 0.05 to 3.0% by weight of a polymerizable monomer having a carboxyl group of a dibasic acid,
(D) 27.3 to 40.0 wt% filler, and
(E)-(2) 0.1 to 1.0% by weight of a chemical polymerization initiator and / or a photopolymerization initiator
A dental two-paste self-adhesive composite resin cement that contains no paste and no water.